CN106928053A - A kind of method that oxidative lignin is degraded into small molecule aromatic compound - Google Patents
A kind of method that oxidative lignin is degraded into small molecule aromatic compound Download PDFInfo
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Abstract
A kind of method that oxidative lignin is degraded into small molecule aromatic compound, belongs to biomass degradation technical field, and in particular to a kind of organic procedures being catalyzed by nontransition metal are broken C C keys, and oxidative lignin is degraded into the method for small molecule aromatic compound.Oxidative lignin is oxidized agent oxidation in organic solvent first, the intermediate product that will be obtained again alcoholysis or hydrolysis in the presence of catalyst, obtain small molecule aromatic compound, such as benzoic acid of methoxy substitution, the phenol of methoxy substitution, the benzoic ether of methoxy substitution, chain alcohol.The present invention has step simple, reaction condition is gentle, high conversion rate (up to 100%), without transition metal the advantages of, there is effect to various connecting modes of oxidative lignin, high selectivity, the purpose of efficiently lignin degrading can be reached, is conducive to its large-scale industrialization application.
Description
Technical field
The invention belongs to biomass degradation technical field, and in particular to a kind of organic procedures being catalyzed by nontransition metal
Fracture C-C keys, oxidative lignin is degraded into the method for small molecule aromatic compound.
Background technology
With the continuous propulsion of China's Development of China's Urbanization, energy demand sustainable growth, energy supply and demand contradiction is also increasingly dashed forward
Go out, it is the justice that should have of energy sustainable development to tap a new source of energy with regenerative resource.Biomass resource is extremely abundant, clear
Clean renewable resource.Lignocellulosic is transformed by green plants through photosynthesis, and source is wide, cheap, is non-food
The renewable biomass resources of species.Global annual about 17,000,000,000 tons of the lignocellulosic produced through photosynthesis, but its utilization
It is less than the 1% of total amount, great exploitation potential.
Lignocellulosic mainly includes three parts：Cellulose (accounting for 30-50%), hemicellulose (accounting for 20-35%) and
Lignin (accounts for 20-35%).The natural reserves of lignin (Lignin) are only second to cellulose, and are that nature uniquely contains virtue
The non-fossil base resource of base.The annual whole world is up to 6,200,000,000 tons by the lignin that plant growth is produced, but is seldom utilized, and surpasses
95% lignin is crossed still mainly as the discarded object of industrial slurrying, is burnt after being directly discharged into rivers or concentration with waste water, made
Into serious environmental pollution.It is in the past few decades, lignin conversion is very big for the research of macromolecular material is achieved
Progress.But with the continuous reduction of fossil energy, lignin degrading obtains high valuable chemicals increasingly by people's
Concern, as efficiently using one of most potential mode of lignin.
The complicated structure of lignin and inert chemical bond cause that its degraded is extremely difficult.At present, the degraded master of lignin
Concentrate in the fracture of C-O keys and C-C keys.Wherein, by the fracture of C-C keys come the research of lignin degrading it is main or with
Based on transition-metal catalyst, and effect is not very good.Additionally, transition-metal catalyst catalytic process condition is harsh
There is metal residual in (inert atmosphere or HTHP etc.) and reaction, its work is limited to a certain extent after terminating
Industry application.In view of the deficiency of above transition-metal catalyst, the exploration of nontransition metal catalyst system and catalyzing is as inevitable.
2011, the bond energy that Beckham etc. has reported C-O keys in lignin dimer was 65.2kcal/mol, if by α-
OH is oxidized to ketone (oxidative lignin, ligninox) after, its bond energy be reduced to 55.9kcal/mol (J.Phys.Chem.Lett.,
2011,2,2846–2852).Using this conclusion, the fracture of nonmetal catalyzed C-O keys have been reported (Nature, 2014,515,
249–252；Angew.Chem.,Int.Ed.,2015,54,258–262；Green Chem.,2016,18,2029–2036).If
Can be substrate using oxidative lignin, search out that reaction condition is gentle, economic and environment-friendly, high selectivity fracture C-C keys non-gold
Category catalyst system and catalyzing, it will expand the application category of lignin degradation significantly.
The content of the invention
The technical problem to be solved in the present invention is to overcome the shortcomings of background technology, there is provided a kind of step is simple, reaction bar
The gentle method that oxidative lignin is degraded into small molecule aromatic compound of part, its step is as follows：
(1), the synthesis of oxidative lignin is as follows：Reference literature J.Am.Chem.Soc., 2013,135,6415-6418,
Angew.Chem., Int.Ed., 2015,54,258-262.
1)β-O-4linkage
2)α-O-4linkage
3)β-1linkage
4)α-1linkage
(2), the oxidation of oxidative lignin：Oxidative lignin and oxidant are dissolved in organic solvent, at 20~120 DEG C
Reaction 6~24 hours, reaction solution obtains intermediate product after column chromatography for separation；Oxidative lignin and the consumption mol ratio of oxidant
It is 1：1~4, described oxidant be trifluoro Peracetic acid, 3,5- dinitros benzoyl hydroperoxide, to nitroperoxybenzoic,
Chloroperoxybenzoic acid, peroxyformic acid, benzoyl hydroperoxide, Peracetic acid or hydrogen peroxide etc.；Described organic solvent be dichloromethane,
Tetrahydrofuran, toluene, chloroform, dimethylbenzene or 1,4- dioxane etc.；In organic solvent, the concentration of oxidative lignin for 0.01~
1.00mol/L；
(3), the hydrolysis or alcoholysis of intermediate product：The intermediate product that step (2) is obtained is dissolved in organic described in step (2)
In solvent or alcohol, and catalyst is added, stirring is hydrolyzed and reacts or alcoholysis reaction for 1~6 hour, and product is through column chromatography point
Small molecule aromatic compound, such as benzoic acid of methoxy substitution, the phenol of methoxy substitution, the benzene of methoxy substitution are obtained after
Formic acid esters, chain alcohol etc.；Described catalyst is the acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or NaOH, potassium hydroxide, potassium carbonate, carbon
The alkali such as sour sodium, sodium acid carbonate, catalyst is 0.01~0.2 with the consumption mol ratio of described intermediate product：1；Described hydrolysis
Reaction is carried out at 20~100 DEG C, and described alcoholysis reaction is carried out at 20~80 DEG C, described alcohol be methyl alcohol,
Ethanol, isopropanol, n-butanol, benzylalcohol etc..
It is of the present invention it is a kind of oxidative lignin is degraded into the method for small molecule aromatic compound, described oxidation
Lignin is the dimer containing following structure, tripolymer, polymer and natural lignin.
Beneficial effects of the present invention：
1st, system of the invention is easy to operate, reaction condition is gentle, high conversion rate (up to 100%), without transition metal
Catalyst.
2nd, inert C-C keys are converted into the present invention C-O keys of the ester of easy fracture using oxidation reaction, can indirectly realize wood
The fracture of quality C-C keys.
3rd, system of the invention has effect to various chemical bonds of lignin, and can high selectivity, efficiently degrade
Lignin and polymer, are conducive to the heavy industrialization application of lignin degradation.
Specific embodiment
The present invention can be further illustrated by following examples, embodiment is to illustrate the invention without limitation originally
Invention, protection scope of the present invention is not restricted to this.
Embodiment 1
(1) substrate oxidation lignin dimer 1 (1.211g, 1eq.), oxidant m-chloro mistake are added in 250mL round-bottomed flasks
Oxybenzoic acid (m-CPBA) (1.73g, 2eq.), dichloromethane 150mL is dissolved, and is stirred at room temperature 12 hours.Column chromatography (oil
Ether) obtain colorless oil acetal 1a (1.12g, yield 98%).Nuclear magnetic resonance data：
1H NMR (500MHz, Chloroform-d) δ 8.07 (dd, J=8.3,1.3Hz, 2H), 7.58 (t, J=7.3Hz,
1H), 7.44 (t, J=8.0Hz, 2H), 7.35-7.31 (m, 2H), 7.12 (d, J=8.5Hz, 2H), 7.07 (t, J=7.3Hz,
1H),6.03(s,2H)；13C NMR(126MHz,CDCl3)δ165.6,157.1,133.6,130.0,129.8,129.5,
128.6,122.9,116.3,86.4.
(2) step (1) oxidation product-acetal 1a (0.57g, 2.5mmol) is added to be dissolved in tetrahydrochysene in 250mL round-bottomed flasks
In THF solvent, add the hydrochloric acid solution (0.5mL) of 1mol/L to make catalyst, stir 6 hours at room temperature.Column chromatography (acetic acid second
Ester：Petroleum ether=1:10, volume ratio) obtain product as white solid benzoic acid (0.25g, yield 83%), colourless liquid phenol
(0.21g, 88%).Nuclear magnetic resonance data：
Benzoic acid1H NMR(400MHz,CDCl3) δ 7.49 (t, 2H, J=7.5), 7.63 (t, 1H, J=6.8), 8.15 (d,
2H, J=8.4)；13C NMR(100MHz,CDCl3)δ128.4,129.6,130.1,133.7,172.1.
Phenol1H NMR(400MHz,CDCl3):δ 7.24 (dd, J=8.8,7.2Hz, 2H), 6.93 (t, J=7.2Hz,
1H), 6.83 (d, J=8.4Hz, 2H), 5.02 (s, 1H)；13C NMR(100MHz,CDCl3):δ155.6,129.8,120.9,
115.4.
Embodiment 2
(1) it is hydrogen peroxide (H to change oxidant2O2) (2eq.), the step of other conditions such as embodiment 1 (1), obtain colourless
Grease 1a (1.10g, yield 96%).
Nuclear magnetic resonance data：Such as embodiment 1.
(2) change (2) the step of solvent is methyl alcohol, other conditions such as embodiment 1, obtain colourless liquid methyl benzoate
(yield 98%) and colourless liquid phenol (yield 90%).
Nuclear magnetic resonance data：
Methyl benzoate1H NMR(CDCl3,400MHz):δ 8.04 (d, J=7.6Hz, 2H), 7.55 (t, J=7.4Hz,
1H), 7.43 (t, J=7.8Hz, 2H), 3.92 (s, 3H)；13C NMR(CDCl3,100MHz):δ167.1,132.9,130.1,
129.5,128.3,52.0.
Phenol such as embodiment 1.
Embodiment 3
(1) change (1) the step of substrate is 2 in above formula, other conditions such as embodiment 1, obtain red oil 2a and (produce
Rate 30%) and white solid 2b (yield 65%).
Nuclear magnetic resonance data：
2a 1H NMR(500MHz,CDCl3) δ 7.70 (dd, J=8.5,2.1Hz, 1H), 7.51 (d, J=2.1Hz, 1H),
7.13-7.07 (m, 1H), 7.03 (td, J=7.8,1.6Hz, 1H), 6.88 (dd, J=8.2,1.5Hz, 1H), 6.83 (dt, J=
9.2,3.4Hz, 2H), 6.59 (dd, J=5.9,4.1Hz, 1H), 4.06 (dd, J=11.9,5.9Hz, 1H), 3.98 (dd, J=
11.9,4.2Hz, 1H), 3.88 (d, J=6.3Hz, 6H), 3.80 (s, 3H), 3.48 (s, 1H)；13C NMR(126MHz,CDCl3)
δ165.07,153.43,150.77,148.62,145.23,124.72,124.13,121.61,121.04,120.08,
112.28,112.11,110.28,97.32,63.17,55.96,55.94,55.77.
2b 1H NMR(500MHz,CDCl3) δ 7.15-7.02 (m, 2H), 6.97-6.87 (m, 2H), 6.81 (d, J=
8.4Hz, 1H), 6.67-6.60 (m, 2H), 4.90 (t, J=4.3Hz, 1H), 4.20 (d, J=4.4Hz, 2H), 3.89-3.79
(m,27H),3.61(s,1H)；13C NMR(126MHz,CDCl3)δ168.64,150.60,149.40,147.08,146.78,
143.92,124.04,121.16,118.82,112.66,112.46,111.17,105.53,80.71,63.26,56.17,
56.02,55.91.
(2) (2) the step of oxidation product is 2a, other conditions such as embodiment 1 are changed.Obtain white solid 3,4- dimethoxies
Yl benzoic acid (yield 63%) and light yellow liquid o-methoxyphenol (yield 66%).
Nuclear magnetic resonance data：
3,4- dimethoxybenzoic acids1H NMR(400MHz,CDCl3) δ 10.47 (br.s, OH), 7.78 (dd, J=8.4,
1.8Hz, 1H), 7.60 (d, J=1.7Hz, 1H), 6.92 (d, J=8.5Hz, 1H), 3.95 (s, 3H), 3.95 (s, 3H)；13C
NMR(100MHz,CDCl3)δ171.9,153.8,148.7,124.6,121.7,112.438,110.4,56.1,56.0.
O-methoxyphenol1H NMR(500MHz,CDCl3) δ 6.93 (dq, J=6.5,2.3Hz, 1H), 6.91-6.81 (m,
3H),5.64(s,1H),3.88(s,3H)；13C NMR(126MHz,CDCl3)δ146.61,145.68,121.48,120.18,
114.58,110.77,55.89.
(3) it is 2b, the other conditions such as step of embodiment 1 (2) to change oxidation product.Obtain white solid 3,4- dimethoxys
Phenol (yield 73%) and (3- hydroxyls -2) -2- methoxyphenoxypropionic acids (yield 67%).
Nuclear magnetic resonance data：
3,4- syringol1H NMR(400MHz,CDCl3)δ3.85(s,3H),3.87(s,3H),4.58(b s,
1H), 6.36 (dd, 1H, J=7.6Hz, J=2.8Hz), 6.49 (s, 1H), 6.75 (d, 1H, J=7.2Hz)；13C NMR
(101MHz,CDCl3)δ55.9,56.6,100.6,105.7,112.3,142.8,149.7,150.3.
(3- hydroxyls -2) -2- methoxyphenoxypropionic acids1H NMR(300MHz,CDCl3) δ 7.24 (dd, J=5.6,
3.8Hz, 1H), 6.99 (dd, J=5.6,3.9Hz, 1H), 6.89 (dd, J=5.6,3.8Hz, 2H), 4.45 (ddd, J=12.3,
6.9,5.5Hz, 1H), 4.26 (t, J=6.8Hz, 1H), 4.08 (ddd, J=12.3,6.9,5.5Hz, 1H), 3.88 (s, 3H),
2.96 (t, J=5.5Hz, 1H)；13C NMR(75MHz,CDCl3)δ173.39,150.92,147.72,121.53,120.95,
118.03,113.50,76.79,62.51,56.17.
Embodiment 4
(1) it is 2 in above formula to change substrate, and change oxidant is hydrogen peroxide (H2O2), the step of other conditions such as embodiment 1
Suddenly (1), red oil 2a (yield 37%) and white solid 2b (yield 44%) is obtained.
Nuclear magnetic resonance data：Such as embodiment 3.
(2) it is 2a to change oxidation product, and change solvent is methyl alcohol, and the other conditions such as step of embodiment 1 (2) obtains white
Solid 3,4- syringol (yield 96%) and light yellow liquid (3- hydroxyls -2) -2- methoxyphenoxypropionic acid methyl esters
(yield 93%).
Nuclear magnetic resonance data：
3,4- dimethoxybenzoic acid 2- oxoethyl esters1H NMR(500MHz,Chloroform-d)δ9.66(s,1H,
CHO), 7.70 (dd, J=8.5,1.5Hz, 1H, Ar), 7.52 (d, J=2.0Hz, 1H, Ar), 6.85 (d, J=8.5Hz, 1H,
Ar),4.80(s,2H,CH2),3.89(s,3H,OCH3),3.87(s,3H,OCH3).13C NMR(126MHz,CDCl3)δ196.2,
165.8,153.6,148.8,124.2,121.3,112.2,110.4,69.0,56.12,56.08.
O-methoxyphenol such as embodiment 3.
(3) it is 2b to change oxidation product, and change solvent is methyl alcohol, and the other conditions such as step of embodiment 1 (2) obtains white
Solid 3,4- syringol (yield 96%) and light yellow liquid (3- hydroxyls -2) -2- methoxyphenoxypropionic acid methyl esters
(yield 93%).
Nuclear magnetic resonance data：
(3- hydroxyls -2) -2- methoxyphenoxypropionic acid methyl esters1H NMR(300MHz,CDCl3) δ 7.21 (dd, J=5.6,
3.9Hz, 1H), 6.93 (ddd, J=23.0,5.6,3.9Hz, 3H), 4.41 (ddd, J=12.1,6.8,5.5Hz, 1H), 4.24
(t, J=6.8Hz, 1H), 4.10 (ddd, J=12.1,6.9,5.4Hz, 1H), 3.86 (d, J=9.0Hz, 6H), 2.96 (t, J=
5.5Hz,1H)；13C NMR(75MHz,CDCl3)δ169.34,150.92,147.72,121.53,120.95,118.03,
113.50,76.85,62.26,56.17,52.82.
3,4- syringol such as embodiment 3.
Claims (4)
1. a kind of method that oxidative lignin is degraded into small molecule aromatic compound, its step is as follows：
(1) oxidation of oxidative lignin：Oxidative lignin and oxidant are dissolved in organic solvent, 6 are reacted at 20~120 DEG C
~24 hours, reaction solution obtained intermediate product after column chromatography for separation；Oxidative lignin is 1 with the consumption mol ratio of oxidant：1
~4, described oxidant is trifluoro Peracetic acid, 3,5- dinitros benzoyl hydroperoxide, to nitroperoxybenzoic, m-chloro peroxide
Benzoic acid, peroxyformic acid, benzoyl hydroperoxide, Peracetic acid or hydrogen peroxide；In organic solvent, the concentration of oxidative lignin is 0.01
~1.00mol/L；
(2) hydrolysis or alcoholysis of intermediate product：The intermediate product that step (1) is obtained is dissolved in the organic solvent described in step (1)
Or in alcohol, and catalyst is added, stirring is hydrolyzed and reacts or alcoholysis reaction for 1~6 hour, and product is after column chromatography for separation
Obtain small molecule aromatic compound；Described catalyst is hydrochloric acid, sulfuric acid, phosphoric acid, NaOH, potassium hydroxide, potassium carbonate, carbon
Sour sodium or sodium acid carbonate, catalyst are 0.01~0.2 with the consumption mol ratio of described intermediate product：1；Described hydrolysis
Carried out at 20~100 DEG C, described alcoholysis reaction is carried out at 20~80 DEG C.
2. a kind of method that oxidative lignin is degraded into small molecule aromatic compound as claimed in claim 1, its feature exists
In：Organic solvent described in step (1) is dichloromethane, tetrahydrofuran, toluene, chloroform, dimethylbenzene or 1,4- dioxane.
3. a kind of method that oxidative lignin is degraded into small molecule aromatic compound as claimed in claim 1, its feature exists
In：Alcohol described in step (2) is methyl alcohol, ethanol, isopropanol, n-butanol or benzylalcohol.
4. a kind of method that oxidative lignin is degraded into small molecule aromatic compound as claimed in claim 1, its feature exists
In：Oxidative lignin described in step (1), its structural formula is one of following shown,
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721814A (en) * | 2017-09-18 | 2018-02-23 | 吉林大学 | Pass through the method for nucleophilic substitution lignin degrading and lignin model compound |
| CN112480182A (en) * | 2020-12-22 | 2021-03-12 | 南京林业大学 | Preparation method of low-molecular-weight lignin and application of low-molecular-weight lignin in preparation of monophenol compounds |
| CN112979414A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
| CN113365968A (en) * | 2019-01-31 | 2021-09-07 | 有机燃料瑞典公司 | Method for producing oxidized wood products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844360A (en) * | 2010-02-10 | 2012-12-26 | 德累斯顿工业大学 | Substrate for soil improvement having a water-storing property, method for producing same, and use thereof |
| CN105693483A (en) * | 2016-01-14 | 2016-06-22 | 淮阴师范学院 | Method for adsorptive separation of aromatic aldehyde in lignin oxidized liquid |
-
2017
- 2017-05-03 CN CN201710302461.8A patent/CN106928053A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844360A (en) * | 2010-02-10 | 2012-12-26 | 德累斯顿工业大学 | Substrate for soil improvement having a water-storing property, method for producing same, and use thereof |
| CN105693483A (en) * | 2016-01-14 | 2016-06-22 | 淮阴师范学院 | Method for adsorptive separation of aromatic aldehyde in lignin oxidized liquid |
Non-Patent Citations (1)
| Title |
|---|
| 李小红，邹树良: "《过氧酸高选择性氧化木质素β-O-4型二聚体化合物》", 《食品科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107721814A (en) * | 2017-09-18 | 2018-02-23 | 吉林大学 | Pass through the method for nucleophilic substitution lignin degrading and lignin model compound |
| CN113365968A (en) * | 2019-01-31 | 2021-09-07 | 有机燃料瑞典公司 | Method for producing oxidized wood products |
| CN112979414A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
| CN112979414B (en) * | 2019-12-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compound from lignin |
| CN112480182A (en) * | 2020-12-22 | 2021-03-12 | 南京林业大学 | Preparation method of low-molecular-weight lignin and application of low-molecular-weight lignin in preparation of monophenol compounds |
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Application publication date: 20170707 |